Method for-separating mixtures of liquids



E. l. DYER ET AL METHOD FOR SEPARATING MIXTURES OF LIQUIDS July 15.1

original Filed'June 15, 1'914 2 sheen-sn. 2

dij. ,a

El. er Algeaise Reuma July 15, 1924.

` vRe.. 15,871

UNITED; STATES PATENT womer.

l ERNEST I. DYER, OF BEVERLEY mLLS, AND ARTHUR. Bt HEISE, OF BEDONIO, CALIFORNIA. k l

METHOD Foa-SEPARATING mrx'runasor LIQUrDs.

Original No. 1.242,784, dated October 9, 1917, Serial No. 845,060, led June Areissue tiled September 13, l1923. Serial No. 662,563.

To all whom it may concern.'

' -Be it known that we, ERNEST I. DYER and ARTHUR AR. H-EisE, citizens of the United States, residing, the said DYER at Beverley Hills,"in the county of Los Angeles and State of California, and the said Hnrs'i: at Redondo, county of Los Angeles and State of California, have invented certain 'new and useful Improvements in Methods for Separatin Mixtures of Liquids, of which the following isa specification.

This invention relates `to the art of'separating -mechanical mixtures of liquids such as emulsions of oil and Water, and particularly `to those peculiarly stable .and refractory emulsions which occur in connection with the asphaltic petroleums of California. While the process hereinafter describedl is applicable to the treatment of hydrocarbon oils in general, it is more especially designed for the treatment of petroleum emulsions of the type mentioned, and in the following description of our process, for the-sake of clearness, its adaptation to such oils will be explained, but it must be understood that we do not limit ourselves to this application alone.

The asphaltic crude oils of California are especially liable to carry water in the form of aneinulsion which cannot be read'- ily and economically separated from the oil bysettling, .moderate heating, blowing with air or by the'application of the other well known means usually resorted to for such purposes. Several methods have been developed which are suitable for use under proper conditions,l but as far as we know,

none as yet has been developed which possesses such characteristics as render it' suitable for use under a great variety of adverse circumstances.

It has been -rognized for some time, in connection with the oil industry, that it would be highly desirable to develop a simple, .economical and safe method for breaking down these refractory emulsions by mechanical means alone.: It is' well known that the water is contained in the oil in the 15, i914. Application for great tenacity. yIn some cases their form may be accounted for by well knownycapillary' effects due to the surface tension existing between the interfaces of non-miscible liquids; in others, laboratory experiments tend to show that the globules of Water are actually surrounded by a tenacious envelop composed largely of specific gravity than the mean specific gravity of the oil itself. It may be com osed of heavy asphaltic substances derived rom the oil, such as so called asphaltenes or of any other substances present in the o il whether or not of Origin foreign -to that of the oil itself. Whatever the composition of this envelop may be or whether it may be onl a capillary film of the water or of the oil or both, We have discovered that the water substances of greater cannot be completely separated from the oil eliminating some of the Water, but their "lack of effectiveness has been such that their application has never been extensive. Electrical methods have been dependedfor their `action on imparting electrical charges to the suspended particles, causing them to coalesce, butl ,these methods have not as yet found great favor in the oil fields. I l

The present method lfor the successful treatment of the petroleum emulsion for breaking down 'the envelop, whether it be an actual physical membrane made up of substances ofcomposition'diiferent from the oil itself orderived from the oil, or merely a film eitherl of 'oil Orilof water, is to subject the flowing body of oil under treatment to such pressures as to force the oil through sages of such dimensions thatdistortion of -the form of the globule with subsequent rupture of the skin necessarily results. This change of form tends lbrium in the case of capillary films due to surface tension and inthe case of actual physical envelops as above described, to 'set up bothV tangential andradial stresses suchI that'in either-case rupture will ensue; and inasmuch. as such rupture will then take place in a space of capillary dimensions all sucli rupturing globules willbe within such developed which i to destroy the equiy a short distance of each other as to enable Vthe cohesive or capillary forces to cause sphere has the largest volume for the least Vextent of surface and this is the form assumed by particles of .one liquid suspended freely in another when in a state of Vequilibrium. In order, therefore, to destroy the equilibrium of the envelop, it becomes necessary to change .the form ofthe globule, for by so changing the-form the extent of surface necessary to inclose a given mass is increased and stresses are set up in the envelop or capillary film tending to destroy the equilibrium, and if a time limit is introduced such that the change ofl form takes place during a period so short as Ato make itv impossible for the film to stretch yor readjust itself' to the lnew form by migrations of particles from other portions of the film, the kfilm will break and as the disruption occurs in the presence of and within capillary reach of other and pimilar particles, c'oalescence of the-ir contents Will re sult.

In the case of dense particles, originally -spherical in form, are in contact, the figure assumed by them is polyhedral in a state of'equilibrium. These polyhedra being forced into a capillary passage are subjected to unsymmetrical forces through friction, impact, capillary action or other causes with attendant destruction of their envelops, the result being the same as action, frictional resistance, theviscosity of the liquid itself or other causes. As a consequence, in forcing a mixture of oil and Water through a very small opening, the tendency is for the two components of the mixture to move at ldiierent velocities, so' that certain port-ions of the stream may become relatively rich in water and others rich in oil. This tendency facilitatesthe separation of the two liquids after rupture of the envelops in the case of emulsions and at the same time tends to prevent their reemulsification.

By practical experiments, as' we have proven, emulsions of water and oil can be ed is forced through a multiplicity of capil permanently broken down in the mann'er de-A scribed and the water contained in the disrupted'globules completely separated from the oil.

The owingbody of emulsion to be treatlary passages of a capillary medium, )vhich medium may be 'provided' in a great many ways. In handling emulsions of many emulsions where the types we use a closelylwoven cloth, any ma bodies through which pass openings `of capillary character, but with oil and 'water mixtures that are more di'licult to handle We use the specific apparatus shown in` Figs. 2 and 3 and more particularly described hereinafter. Thelemulsion may be caused 'to pass through'the capillary body either by means of a pump, elevated tank or other suitable pressure-developing device on the inlet side or by a vacuum pump, siphon or other suitable device for deriving pressures lower than atmospheric on the outlet side. Under certain conditions there may be employed any combination of any of the above means for creating a difference in pressure between inlet and outlet sides of thecapillaly substance.

e have found in carying out our method'... i

that inasmuch as surface tension is decreased by elevation of temperature, tlie4 emulsion may be broken down with greater ease by a heating of the same prior to a forcing thereof under pressure through the vcapillary medium for breaking down the globules to free or liberate the water therein, and further that through lthe same cause the tendency for reemul'sication of the treatedemulsion is minimized, inasmuch as the ability of the water to form an emul` sion with-the oil is diminished due to the apparatus for this purpose, and wherein--- igure 1 isa diagrammatic vview-in elevation of an apparatus forheating the emulf sion for treatment and forcing the same through a connected system of capillary mediums for breaki down or destroying the globules for. liberation of the water contained therein.y

Y Fig. 2 is an enlarged detail sectional View disclosing a system of connected capillary mediums. i

Fig. 3 is a sectional plan View taken onv line Fig. 2 offthe drawings.

In the drawings, the numeral l'is used to designate any suitably constructed or receiving reservoir for thev emulsified 'oil to be treated, which tank maybe elevated' at -a -height above the capillary medium, suffi'- cient to give the desired'pressure for forclos ing the emulsion of oil lthrough the'said capillary medium, but preference is given to the employment of a pump 2. Tank 1 is shown equipped with a steam coil 3, which may be used to decrease the viscosity of the oil and cause a certain amount of the vfree water contained in the emulsion to precipitate out under favorable conditions, and at the same time enable `the oil to flow through the inter-connecting iping 3 with ater facility. The emu sion flowing t ough the pi ing 3 is conveyed to a heater. 4 of or inary construction, so arranged as to heat the emulsified oil, in the case of the exam l'e shown, by vmeans of the exhaust steam m 'the pump 2 delivered thereto by the connecting ipe 4'.. `This heater may be used indepen ently of coil 3 or in con'unction with it, and may be also furnish with live steam or any other, suitable heatin medium. From thepump 2 the emulsifi oil is forced through a connection `5 to any. suitably constructed form of a capillary separator 5. In this illustration of the separator is disclosed a diagrammatic representation of an apparatus resembling a .filter press of conventional form and construction. As this form of a paratus is well 'understood a detailed esciilption will not be necessary. In gener it will be seen to consist of a series of frames 62 claped together by means of a screw 7, in su a way that the emulsied oil flowing from the connection 5 is caused to enter by opening 8, following the course indicatedl by the arrows. 'Durin its passage through the apparatus it is force un er pressure through the interstices .of the capillary mediums, each consisting of a layer or a cake 9 of mineral material, such as infusorial earth on the outer surface of a cloth 9' which backed b a screen or perforated plate 10, which p ate serves to reinforce the cloth and prevent itstearing and at the same time' affords a relatively through it. vAfter passing free o mgthe capillary medium or mediums,

with its water particles or contents freed or liberated from its inclosing envelop, pisses out throu h the o ings 11, into tro a suitab place of-deposit,'such as the tank 14:. This tank 14 is equipped with suitable outlets sothat the water which precipitates out almost immediately may be drained o independently of the `oil from time to time, through the outlet pipe 15, connected with the bottomv of the tank, while the oil rising .within the tank 14 escapes therefrom through the overow outlet. pipe 16,

' connected near the topof the said tank, as

- shown. With 'this arrangement the dried foil. will flow -oontinuousl out of the dischargeoutlet 16, to a suitable place of deposit and the water discharge' through the traversed by bot h 12, an throug the pipe 13, to.

pipe 15.' .The capacity of l the casilla By an extended series of experiments with the most refractory emulsions with which we have had experience, taken from the,I Santa Maria oil fields in California, vwe have been able to effect almost complete separation of the water content with an apparatus of the type illustrated. On apying to the vreceiving or outer surface of the cloth 9 a layer or cake of diatomaceous earth in a finely divided` state, we have found that under some conditions the eectiveness of the operation is increased, so that by careful tests we have been able to remove substantially all of the emulsified water content in the manner described.

The method herein, described for separating mixtures of liquid must not be treated as a process filterm operation, for such is not the case. vIn tration, thev object is to remove a solid or more or less "solid substancel from a liquid, and the substances arel separated by the intervention of a Vporous su stance which is impervious to one of them so that during the filtering operation one substance passes on, leavin the other behind and deposited on the ii tering medium. Under the presentv invention, the primar object is to separate two liquids, es ecia ly an oil and water emulsion.` yBoth o these substances pass to ther through the porous orcapillary me ium, which in this case acts not as a filter or strainer, but as a device for breakin down or, destroying the as descri d, in order to free or liberate the water confined therein, no separation of the liberated water from the oil taking placey until the capillary or porous medium has been entirely and ractically simultaneously liquids Aand vthe -two brought to a state of rest or of motion at relatively low velocity out .of vcontact with lobular partc es of the emulsion.

the porous orcapilla f ,medium In the A case of such oils as may e wet or emulsiiied,

diie to the presence of minute solids `or mineral matter or other forei in a finely divided state,'formmg"a nucleus about which water tends to Agather Aor .be absorbed, the operatioi/imay be facilitated Y by retaining Vsuch substancesjon the capillary medium,l these substances tendingy to take the place of the diatomaceous earth describedpabove when handling oils containing nucleus forming impuritess'althou h in handling oils containi` the so-call ashaltenes we find it pre erred to use the insubstances f orial earth 9. In the case of oils con' taining minute solids the mineral matter' ma act as a positive aidto separation, and

wi such oils the removal of these foreign substances is purel lincidental to the primary function of tie process, so that vsuch filtering action as may occur is of secondaryv consideratiomalthough the removal of these particles, in so far as the presence of water may depend upon them, will tend to prevent reemulsiication.

Owing to the extreme simplicity of the apparatus necessary to apply our process and the moderate pressures which we have found are linquired to force the oil through the capillary openings of the mediums thereof, the cost of construction thereof and of the treatment ofthe emulsified oil is low, and,

appeal to and prove extremely valuable to the small producers of oil who cannot sell their product if it contains an undue moisture. 111 many cases 1t will cantity of possible to carry out the method in connection withtlie oil flowing through pipe lines already existing, so that the 011 may be deprived of its emulsied water content in transitfrom the fields to point of use. At places where oil is used as fuel, and may become contaminated with Water during transport by *.vessel, the process furnishes a ready and inexpensive means of overcoming the difficulties which have heretofore exlsted. On board ship, in power plants and 1n connection with other industrial operationsusing oil lfuel Wherefor some cause or other a supply of wet oil may have been received through inadvertence, this process enables the water to be removed continuously during ordinar every-day operation. The water remove carries with it such salts as may be in solution, rendering the oil suitable for use in refineries without destructive eects on stills and other apparatus. Atthe same time it eliminates trouble in furnaces nand oil Aburners due to clogging through precipitation of salts and in such industrial processes as require heat to be derived4 from a hydrocarbon uncontaminated with such salts, it

provides suitable relief. In the removal of water from valuable'retining oils the plrocess may be conducted in a closed cycle preventing losses by evaporation which are now incidental to all other methods with vwhich we are asfet familiar. Asithe.opera tion is conductsI under relatively low pres- 'suie and at temperatures but slightly excecding the normal and without the `ap lication of electricity at high otentia all,

danger to life and property is o viated.

.'tection by Letters Patent is Having thus described the invention 'what we claim as'new and desire to secure pro-4 1. The method of separating Water from en'iulsiied mineral oils which consists in forcing the water and oil mixture under pressure through infusorial earth and then allowing the water and oil to stratify by gravity.

ereby 2. '1 he method of separatin water from emulsiied mineral oils 'whic' consists in forclng the oil and water mixture under ressure through asupporting backin having thereon a layer of infusorial eart and in allowing the Water and oil so treated to stratify byl gravity. Y

3. The method of separating ywater from eniulsified mineral oils which consists in forcing the oil and-Water mixture under pressure through a woven cloth backing having thereon a layer. of infusorial earth and in allowing the water and oil so treated to `stratii'y by gravity. as a consequence, the descr1bed process will Y water mixture under pressure throu lr a g layer of infusorial earth, and-in then a lowfing the oil and water to stratify by gravity. 6. The method of se arating water 'from' emulsified minera-l oils 1n which Water is the dispersed phase which consists in forcing the water and oil mixture under pressure through a capillary mediumv comprisin mineral matter di'erent from the cause o the emulsion, and in subsequently separat.

ing the oil and the Water by the difference in their specific gravities. o

7. The method of separating Water from emulsified mineral oils in which water is the dispersed phase which consists in forcing the water and oil mixture through a capillary medium comprising a supporting backing having thereon a layer of mineral matter different from the cause of the emulsion, and in subsequently separating the oil and the water by the difference in their specific l gravities.

8. The method of separatin water and solid impurities from oil whic consists m forcing a stream of a natural emulsified mixture containing oil, water, and vsolid impurities under pressure against a body of mineral matter located to obstruct the flow of sad'stream for retaining the solid impurities and ermitting the oil and water to pass, then a. lowing the water and oil to'I strati b avit 9. 'If-lie iheliod'gf se aratin water and solid impurities from oil Whic consists 1n forcing a stream of a natural emulsitied mixture containing oil, water, and solid 1mpurities under pressure against a bod of mineral matter Vessentially dierent rom said solid impurities and located to obstruct the flow of said stream for retaining the solid impurities and ermitting the oil and water to pass, then a oil to stratify by gravity. i

10. The method ofseparating water and solid impurities from 011 which consists in forcing a stream of a natural emulsified.

y v mixture containing oil, water, and solid impurities under ressure against a body of mineral matter eld on a supportin backlng es ecially located for obstructing'the flow o said stream to retain thesolid irnpurities and permit the oil and water to pass, then allowing the water and oil to. strati by gravity. 11.

lowing the water and' e method of separating water from l Y signed our names.

ERNEST I.' DYER.v ARTHUR lR. HEISE. 

